Abstract

The synthesis and characterization of neutral platinum silylene complexes (R3P)2Pt=SiMes2 (R = i-Pr (1) or cyclohexyl (2), Mes = 2,4,6-trimethylphenyl) is reported. The dimesitylsilylene ligand in 2 is displaced by a number of ligands including phosphines, alkenes, alkynes, and O2. Complex 2 reacts with ROH substrates (R = H, Me, Et) to give (Cy3P)2Pt and Mes2Si(OR)(H) and with H2 to give trans-(Cy3P)2Pt(H)SiHMes2 (3). Reaction of H2SiMes2 with (Cy3P)2Pt gave cis-(Cy3P)2Pt(H)SiHMes2 (4). EXSY NMR experiments of 4 reveal that exchange of silicon and platinum hydrides occurs via reductive elimination – oxidative addition and not via a silylene intermediate.Key words: silylene, EXSY, platinum, hydride.

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